Hydrogenation catalyst composition, process for preparing the same and use thereof

ABSTRACT

The present invention relates to a hydrogenation catalyst composition, process for preparing the same and use thereof. The composition comprises a hydrogenation catalyst, an organonitrogen compound in an amount of 0.01%-20% by weight of the catalyst, a sulfiding agent in an amount of 30%-150% by weight of the sulfur-requiring amount calculated theoretically of the hydrogenation catalyst, and an organic solvent in an amount of 0.1%-50% by weight of the catalyst. The preparation process comprises introducing the required substances onto the hydrogenation catalyst in oxidation state. By introduction of the organonitrogen compound, sulfur and organic solvent, the hydrogenation catalyst composition of the present invention may further increase the sulfur-maintaining ratio of the catalyst during the activation, slow down the concentrative exothermic phenomenon, decrease the rate of temperature rise of the catalyst bed layer, and improve the activity of the catalyst. The process of the present invention may be used for the treatment before the application of various hydrogenation catalysts.

TECHNICAL FIELD

The present invention relates to a hydrogenation catalyst composition,process for preparing the same and use thereof. More specifically, thepresent invention concerns a sulfiding agent-containing hydrogenationcatalyst composition, process for preparing the same and use thereof.

BACKGROUND ART

Generally, hydrogenation catalysts, such as hydrorefining catalyst,hydrotreating catalyst and hydrocracking catalyst comprise refractoryoxides, such as alumina, silica-alumina, molecular sieve and the like,as the support, and one or more metals selected from the groupconsisting of molybdenum, tungsten, cobalt and nickel as the activemetal components. Optionally, hydrogenation catalysts may containauxiliary agent components, such as phosphorus, silicon, fluorine,titanium, zirconium, boron and so on. The metal components of thecatalyst produced during the production process are usually present inan oxidation state. In the hydrogenation process, however, the activemetal components of the catalyst have higher reaction properties whenpresenting in a sulfurization state (metals are present in the form ofsulfides, such as Co₉S₈, MoS₂, Ni₃S₂, WS₂ and so on). The catalyst,thereby, needs to be presulfurized and converted to the sulfurizationstate thereof before being used. However, the presulfiding effectsclosely relate to the catalytic properties, and both the presulfidingprocess and the process control are essential.

In the prior art, there are merely two processes for presulfiding thehydrogenation catalyst, i.e. in situ presulfurization and ex situpresulfurization. In situ presulfurization is a process comprisingfeeding the catalyst into a reactor, and sulfiding by introducing asulfiding agent, which is a common process. It has the disadvantage thatthe presulfurization lasts a long period of time, so as to have anadverse effect on the production efficiency. Ex situ presulfurization isa process in which the catalyst has been sulfurized or the sulfidingagent has been present before loading, and no introduction of asulfiding agent occurs after loading the catalyst into the reactor. Ithas the advantage that the presulfurization lasts a short period oftime, so as to improve the production efficiency.

Ex situ presulfurization concerns completely converting the metals onthe catalyst to the sulfurization state thereof and then passivating; oradding a sulfiding agent before feeding the catalyst into the reactor,and then converting the active metals to the sulfurization state thereofin the reactor. Although it is easy to prepare, store, transport andfeed by using said process, there are no sufficient interactions betweenthe sulfiding agent and the catalyst metals, and the sulfiding agenteasily loses and the concentrative thermal release readily occurs duringthe activation after the sulfiding agent-containing presulfidingcatalyst is fed into the rector.

In the ex situ presulfurization of the hydrogenation catalyst, thesulfiding agent is generally selected from the group consisting ofelemental sulfur, organic sulfides, inorganic sulfides, and mixturesthereof. Different addition methods and treatment methods will result indifferent presulfiding effects. Due to low cost and high utilizationratio, the elemental sulfur is used in many techniques as a sulfidingagent. When the elemental sulfur is used, it is usually introduced intothe catalyst in the prior art by sublimation adsorption, meltimpregnation, impregnation via dispersion in an organic solution,directly mixing with solid elemental sulfur powder, and the like.

U.S. Pat. No. 4,943,547 and U.S. Pat. No. 5,215,954 disclose addingelemental sulfur to an oil having a high boiling point or an organicsolvent to produce a suspension beforehand, and then reacting with afresh catalyst, or impregnating with an oil having a high boiling pointor an organic solvent after the powdery elemental sulfur is contactedwith the fresh catalyst. By said process, a certain sulfur-maintainingratio may be achieved, but there is a problem of the concentrative heatrelease during the activation of the catalyst in the reactor. Moreover,the sulfur-maintaining ratio needs to be further improved. U.S. Pat. No.6,077,803 describes dissolving the elemental sulfur and the organicsulfur in a solvent, and introducing elemental sulfur into the catalystin the presence of a stabilizer selected from organic acids, thiols ororganic alcohols, especially glycerine or hexose. But its disadvantagestill lies in the problem of concentrative exothermic phenomenon.

In U.S. Pat. No. 5,786,293, U.S. Pat. No. 5,821,191 and EP352851,inorganic sulfides are as the sulfiding agent. The preparation processby dissolving the elemental sulfur in (NH₃)₂S solution is usually usedtherein. Complicated operation is the main insufficiency. Impregnationneeds to be conducted at least twice so as to achieve some certainsulfur-loading amount, and the last drying must be carried out under aninert atmosphere.

In U.S. Pat. No. 5,017,535, EP 329499, U.S. Pat. No. 4,725,569 andEP130850, thiols, dimethyl sulfides, carbon bisulfide, and other organicsulfides containing 1-20 carbon atoms are used as the sulfiding agent.The elemental sulfur and organic sulfur are used together as thesulfiding agent in U.S. Pat. No. 5,922,638 and U.S. Pat. No. 5,397,756.The application of organic sulfiding agent has the main problem ofhigher amount and price. In addition, there is also some certain problemin transportation and loading process.

CN1107539C discloses contacting hydrocarbon compounds with the catalyst,and ex situ presulfiding with hydrogen and sulfur-containing compounds.Due to the presence of hydrogen and higher temperature (330° C. in theexamples), the sulfides decompose to produce hydrogen sulfide (in fact,hydrogen sulfide is directly used in said patent). Hydrogen sulfidereacts with the metals on the catalyst to produce the metal sulfides,which is a process of complete presulfurization of the catalyst.However, the presulfurized catalyst easily combusts spontaneously, andthere is safety problem in storage, transportation and loading.CN1400056A describes coating a sulfiding agent-containing presulfidingcatalyst with an oxygen-containing organic compound containing at least16 carbon atoms, treating at a temperature higher than 175° C. for acertain period of time, and then activating with hydrogen so as toreduce the self-heating of the catalyst. However, said process does notcompletely solve the self-heating problem of the catalyst insulfurization state, and there is still a certain problem in storage,transportation and loading of the catalyst. CN1262305A discloses aprocess for presulfiding a hydrogenation catalyst, comprising mixingrubber sulfiding auxiliary agents, olefin-containing components,elemental sulfur and hydrogenation catalysts together, wherein rubbersulfiding auxiliary agents promote the combination of elemental sulfurwith olefin-containing components and reduce the lose of sulfur.However, said patent does not solve the problem of concentrative heatrelease during the activation. U.S. Pat. No. 6,059,956 (CN1076635C)describes introducing elemental sulfur and organic polysulfides into thecatalyst in the presence of olefin- or olefin fraction-containingcomponents such as vegetable oil, then activating with hydrogen, andfinally passivating with oxygen-containing gas. Said patent states thatthe passivation improves the activity of catalyst. However, since themetals on the catalyst are still in sulfurization state, said patentstill has the aforesaid same problems.

SUMMARY OF THE INVENTION

The present invention is put forward in view of the insufficiencies ofthe prior art, aiming to provide a hydrogenation catalyst composition,the process for preparing the same and the use thereof, wherein saidhydrogenation catalyst composition contains a sulfiding agent and anorganonitrogen substance. During the activation, the hydrogenationcatalyst composition of the present invention not only homogeneouslyreleases heat and has a high sulfur-maintaining ratio, but also improvesthe performances of the catalyst, such as activity and the like.

The hydrogenation catalyst composition of the present inventioncomprises

-   -   (1) a hydrogenation catalyst;    -   (2) an organonitrogen compound containing 1-15 carbon atoms in        an amount of 0.01%-20%, preferably 2.0%-10% by weight of the        catalyst;    -   (3) a sulfiding agent which is one or more selected from the        group consisting of elemental sulfur, organic sulfide and        inorganic sulfides, and preferably elemental sulfur, wherein the        sulfiding agent is in an amount of 30%-150%, preferably        55%-120%, most preferably 60%-105% by weight of the        sulfur-requiring amount calculated theoretically of the        hydrogenation catalyst; and    -   (4) an organic solvent in an amount of 0.1%-50%, preferably        2%-45%, most preferably 15%-30% by weight of the catalyst.

The hydrogenation catalyst may be the conventional one, such ashydrorefining catalyst, hydrotreating catalyst, hydrocracking catalystand so on. Generally, the hydrogenation catalyst comprises refractoryinorganic oxides as the support, such as alumina, silica, amorphoussilica-alumina, titanium oxide, molecular sieve, and composite oxides ormixed oxides of several elements. The active metal component is usuallyselected from one or more metals of W, Mo, Ni and Co. And there maycomprise auxiliary agents simultaneously. The selection and amount ofthe hydrogenation catalyst support, active metal component and auxiliaryagent can be specifically determined on the basis of the actualrequirements according to the common knowledge in the art. As forhydrocarbon hydrogenation catalysts, the hydrogenation metal components,based on oxides, generally are in an amount of 1%-90%, usually 3%-50% byweight of the catalyst. The theoretical sulfur-requiring amount of thehydrogenation catalyst is the amount of sulfur required for convertingthe metal components on the catalyst into sulfides (Co₉S₈, MoS₂, Ni₃S₂,WS₂ and so on).

The organonitrogen compound contains 1-15, preferably 2-10 carbon atoms,and it is selected from one or more substances of, for example,hydrocarbyl amines, alcohol amines and amino acids. Specifically, theorganonitrogen compound is selected from one or more substances ofethylene diamine, ethanolamine, diethanolamine, triethanolamine,diisopropanolamine, triethylamine, 2-cyclohexanediamine, trimethylenediamine, triethylene diamine, triethylene tetramine, t-butylamine,dodecyl amine, trioctylamine, ammonium tri-isopropionate, N,N-diethylethanolamine, aminononanoic acid, amino acetic acid, nitrilotriaceticacid, N,N-diethyl hydroxylamine, N-methyl diethanolamine, hexamethylenetetramine, N,N-diisopropyl ethanolamine, acetanilide,N,N-dihydroxyethylaniline, glutamic acid, and other substance(s) havingsimilar structures to said substances above. The organic compoundscomprising simultaneously nitrogen and oxygen, such as amino acids, arepreferred so as to be advantageous to improving the sulfur-maintainingratio and solving the problem of concentrative exothermic phenomenon.

The organic solvent can be selected from the common organic solvents inthe field, e.g. one or more substances of hydrocarbon oils and organiccarboxylic esters. The hydrocarbon oils are selected from one or moresubstances of naphtha, gasoline, kerosene, diesel oil, white oil, lubebase oil, distilled and vacuum heavy distillate oil, preferablyhydrocarbon oils obtained by secondary processing, e.g. hydrocarbon oilsobtained by catalytic cracking process, thermal cracking process and soon. Organic carboxylic esters are organic carboxylic esters containingfrom 6-60 carbon atoms, preferably fatty acid glycerides, such as sesameoil, safflower seed oil, corn oil, cottonseed oil, peanut oil, rape-seedoil, bean oil, walnut oil, coconut oil, olive oil, sunflower seed oil,lard oil, n-butyl acetate, propylene glycol acetate monomethyl ether,1,4-butanediol diacrylate, isopropyl cyclohexanoate,hexamethylene-diisocyanate, triethyl phosphate, methyl phenylacetate,isobutyl phenylacetate, diisononyl terephthalate, dimethyl phthalate,diethyl phthalate, methyl o-hydroxybenzoate, and butylp-hydroxybenzoate, and one or more other organic carboxylic esters inthe class. Hydrocarbon oils and organic carboxylic esters may be usedseparately, or used in combination. If they are mixed together, theweight ratio of hydrocarbon oils to organic carboxylic esters may be1:15-15:1. Preferably, they are mixed together since it is advantageousto solving the problem of concentrative exothermic phenomenon.

The catalyst composition may contain other additives, such as one ormore substances selected from organic carboxylic acids, organicalcohols, organic ketones. For example, the catalyst composition maycomprise organic carboxylic acids containing 2-25 carbon atoms, and saidorganic carboxylic acids are in an amount of 0.5%-15% by weight of thecatalyst.

In addition, the organic sulfide may be one or more selected fromsulfones, thiols, thioethers, thiocarboxylic acids, thirams and organicpolysulfides, specifically one or more selected from dimethyl sulfide,thioacetic acid, tert-dodecyl mercaptan, mercaptoacetic acid,mercaptopropionic acid, mercaptoamino acid, mercaptoethanol and thelike. The inorganic sulfides may be one or more selected from ammoniumsulfide, ammonium hydrosulfide, carbon bisulfide, and the like.

The process for preparing the hydrogenation catalyst composition of thepresent invention comprises the steps of

-   -   (1) supporting the organonitrogen compounds, preferably        containing oxygen and nitrogen simultaneously onto the        hydrogenation catalyst in oxidation state, wherein the        organonitrogen compounds are in an amount of 0.5%-20%,        preferably 2.0%-10% by weight of the catalyst; and    -   (2) supporting the organic solvent and sulfiding agent onto the        hydrogenation catalyst containing the organonitrogen compounds        in step (1), wherein the sulfiding agent is in an amount of        30%-150%, preferably 55%-120%, most preferably 60%-105% by        weight of the theoretical sulfur-requiring amount of the        hydrogenation catalyst, and the organic solvent is in an amount        of 0.1%-50%, preferably 2%-45%, most preferably 15%-30% by        weight of the hydrogenation catalyst. Sulfiding agent-containing        hydrogenation catalysts can be obtained by said process.

The optional step (3) is to heat-treat the sulfiding agent-containinghydrogenation catalyst obtained in said step (2) for 0-20 h, preferably0.2-15 h at 100-130° C., then for 0.2-15 h at 130-180° C., and finallyfor 0-15 h, preferably 1-8 h at 180-300° C.

The organonitrogen compounds in step (1) can be supported with theimpregnating method, or be directly introduced onto the hydrogenationcatalyst. If the impregnating method is used, the organonitrogencompounds are formulated into an aqueous solution, ammonia solution ororganic solution; the hydrogenation catalyst is impregnated into saidsolution, and then dried to remove water, ammonia or organic solvent toobtain the hydrogenation catalyst supported with the organonitrogencompounds. The concentration of the ammonia solution which is generallynot limited is just sufficient to smoothly dissolve the selectedsubstance, and the weight concentration thereof is usually 0.1%-25%. Theorganic solvent is an organic solvent having a relatively lower boilingpoint (e.g. lower than 100° C.) and being capable of dissolving saidsubstance, such as ethanol, methanol, ether, benzene, carbontetrachloride and the like, and is selected according to the commonknowledge on the basis of the organic compounds to be dissolved. Thedrying is conducted at a temperature of 80-200° C., preferably 80-140°C. for 1-20 h, preferably 2-8 h. The impregnation method easily makesthe organonitrogen compound homogeneously dispersing on hydrogenationcatalyst, and is a preferable embodiment. Meanwhile, a suitable amountof sulfur-containing compounds capable of being dissolved in saidsubstance or solution, e.g. ammonium sulfide, may be added therein,generally 0.01%-5% by weight of the total weight of the catalyst.

The theoretical sulfur-requiring amount of the hydrogenation catalystmentioned in said step (2) is the amount of sulfur required forconverting the metal components on the catalyst into sulfides (Co₉S₈,MoS₂, Ni₃S₂, WS₂ and so on). In said step (2), the organic solvent andsulfiding agent are supported by any process employed in the prior art,e.g. (1) firstly supporting the sulfiding agent onto the catalyst, thenimpregnating with the organic solvent; (2) dispersing the sulfidingagent into the organic solvent, and then introducing onto the catalyst;or (3) impregnating the catalyst with the organic solvent first, andthen introducing the sulfiding agent.

The heat treatment in said step (3) is conducted to heat treat thehydrogenation catalyst in step (2) supported with the organonitrogencompounds, sulfiding agent and organic solvent under certain conditions.Said heat treatment may be conducted at an absolute pressure of 0.05-1MPa, or generally at a normal pressure. In addition, said heat treatmentmay also be carried out in an inert gas environment, or in an oxygenatmosphere having an oxygen content of 0.1 v %-30 v %. A mobileatmosphere may also be used therein, but a forcing mobile atmosphere isgenerally not necessary. An immobile atmosphere or a naturally mobileatmosphere may also be used therein.

The sulfiding agent-containing hydrogenation catalyst composition of thepresent invention may be used for the hydrogenation of variousmaterials, e.g. hydrorefining process, hydrocracking process andhydroupgrading process of hydrocarbons according to the properties ofcatalyst. The hydrogenating process comprises the steps of:

-   -   (A) loading the hydrogenation catalyst composition of the        present invention into a reactor;    -   (B) activating the hydrogenation catalyst; and    -   (C) contacting a hydrocarbon oil and hydrogen with the        hydrogenation catalyst under suitable conditions to hydrogenate        the hydrocarbon oil.

The activation in step (B) is conducted under the conventionalactivation conditions of, generally, a pressure of 1-20 MPa, an hydrogenhourly space velocity of 100-30,000 h⁻¹, a rate of temperature rise of5-100° C./h, a final temperature at the inlet of the reactor of 200-400°C., wherein said temperature is maintained for 2-36 h. In addition, oneor more distillate oils from gasoline, kerosene and diesel oil may beadded at any time during the activation, wherein the liquid hourlyvolume space velocity of the distillate oils is 0.2-20 h⁻¹, and theH₂/oil volume ratio is 100:1-2,000:1.

The hydrogenation in step (C) is carried out under the conventionalhydrogenating conditions in the field, which are different from eachother according to different reactions. Generally, it is conducted at apressure of 1-20 MPa, a temperature of 100-450° C., an H₂/oil volumeratio of 50-3,000, and a liquid hourly volume space velocity of 0.1-30h⁻¹. Said hydrocarbon oil may be various hydrocarbon oil, such asgasoline fraction, kerosene fraction, diesel oil fraction, vacuum gasoil or residual oil.

The introduction of the organonitrogen compound, organic solvent andsulfiding agent into the hydrogenation catalyst of the present inventioncould effectively solve the problem of low sulfur-maintaining ratio andconcentrative heat release during the activation of the hydrogenationcatalyst containing only the organic solvent and sulfiding agent. Inaddition, the application of the organic compounds containing oxygen andnitrogen simultaneously is more advantageous to improving thesulfur-maintaining ratio of the catalyst and slowing down theconcentrative heat release, and has more prominent effects. Thehydrogenation catalyst of the present invention can sufficientlyincrease the vulcanizing effects of the catalyst, so as to improve thehydrogenating properties of the catalyst, e.g. hydrodesulfidingactivity, hydrodenitrifing activity, hydrosaturating performance and thelike. The sulfiding agent-containing hydrogenation catalyst obtained theprocess of the present invention has no self-ignitenition, and is easilyto be stored, transported and used. In addition, the catalystcomposition of the present invention has the advantages of simplepreparation procedure, low production cost and being suitable for largescale application.

During the ex situ presulfurization of the hydrogenation catalyst of thepresent invention, a small amount of the organonitrogen compound issupported onto the surface of the catalyst in oxidation state, and thesulfiding agent and organic solvent are then supported thereon, and theheat treatment is finally conducted. By experiments, it shows that thesulfiding agent-containing presulfurized catalyst obtained by suchtreatment has the performances of high sulfur-maintaining ratio, noconcentrative heat release, and high catalytic property during theactivation. The sulfiding agent is supported by the method of thepresent invention, i.e. impregnating the organic solvent first, and thenthe sulfiding agent, which may further solve the problems of lowsulfur-maintaining ratio and concentrative exothermic phenomenon in theprior art. By the pre-heating after the sulfiding agent is supported,especially by step-wise heat treatment of the present invention, thesulfiding agent, organic solvent and metal oxides may form variousstates having different binding extent under different temperaturezones, and the heat release temperature ranges of said differentsubstance-binding states are different from each other during theactivation so that the heat release of the catalyst during theactivation is dispersed in a relatively broad scope, which effectivelyslows down the concentrative heat release and is advantageous to theactivation and application of the catalyst.

After the pretreatment of the catalyst by the present invention, theperformances of the catalyst is obviously superior to those of thecatalyst sulfurized by using the in situ sulfiding process and treatedby the processes in the prior art.

DESCRIPTION OF THE DRAWINGS

FIG. 1 represents the temperature difference curve of the inlet and theoutlet of the catalyst bed layer during the activation of the sulfidingagent-containing hydrogenation catalyst EPRES-2 obtained in Example 2 ofthe present invention.

FIG. 2 represents the temperature difference curve of the inlet and theoutlet of the catalyst bed layer during the activation of the sulfidingagent-containing hydrogenation catalyst C-EPRES-2 obtained inComparative Example 1.

THE PREFERRED EMBODIMENTS OF THE INVENTION

In the following embodiments, some commercially available hydrogenationcatalyst are presulfurized ex situ, which further explains the procedureand effect of the process of the present invention, but does not limitthe scope of the present invention.

Example 1

The commercial hydrodesulfiding catalyst FH-5A (developed by FushunResearch Institute of Petroleum and Petrochemicals, and produced byWenzhou Huahua Group Co.) was used, and the main components andproperties can be found in Table 1.

The specific presulfurization comprises the steps of

-   -   1. homogeneously impregnating triethylamine onto the catalyst        FH-5A in oxidation state, wherein triethylamine is in an amount        of 9% by weight of the catalyst, to form a catalyst supported        with thiethylamine;    -   2. dispersing the elemental sulfur in a solvent in which the        volume ratio of catalytically cracked gasoline to rape-seed oil        is 5:1, wherein the solvent is in an amount of 25% by weight of        the catalyst, and the elemental sulfur is in an amount of 115%        by weight of the sulfur-requiring amount calculated        theoretically amount of the metal-containing catalyst; spraying        the solvent, in which the elemental sulfur is dispersed, onto        the catalyst supported with triethylamine in said step (1); and    -   3. treating the catalyst obtained in said step (2) at a normal        pressure, an immobile air atmosphere, and a temperature of 165°        C., to finally obtain the hydrorefining catalyst EPRES-1        containing the sulfiding agent.

Example 2

The catalyst in oxidation state was the same as that in Example 1, i.e.FH-5A. The specific presulfurization comprises the steps of

-   -   1. dissolving triethylamine and gluconic acid in a weight ratio        of 5:1 in aqueous ammonia containing 10 wt % ammonia to obtain a        solution, impregnating the catalyst in oxidation state with said        solution, wherein said substances are in an amount of 7% by        weight of the catalyst; drying at 120° C. for 5 h, to obtain a        catalyst containing mixed organic additives;    -   2. dispersing the elemental sulfur in a solvent in which the        volume ratio of vacuum gas oil to peanut oil is 1:3, wherein the        solvent is in an amount of 30% by weight of the catalyst, and        the elemental sulfur is in an amount of 90% by weight of the        sulfur-requiring amount calculated theoretically of the        metal-containing catalyst; spraying the solvent, in which the        elemental sulfur is dispersed, onto the catalyst in said step        (1); and    -   3. treating the catalyst obtained in said step (2) at a normal        pressure, a mobile nitrogen atmosphere (wherein the nitrogen        amount is 50 L/L catalyst·h) and a temperature of 140° C. for 4        h, and at a temperature of 270° C. for 2 h, to finally obtain        the hydrorefining catalyst EPRES-2 containing the sulfiding        agent.

Comparative Example 1

The hydrorefining catalyst C-EPRES-2 containing a sulfiding agent wasprepared according to the process in Example 2, wherein said step (1)was cancelled, and step (2) was the same as said step (2). However, saidcatalyst contained no organonitrogen compounds.

Example 3

The catalyst in oxidation state was the same as that in Example 1, i.e.FH-5A. The specific presulfurization comprises the steps of

-   -   1. homogeneously impregnating the catalyst FH-5A in oxidation        state into the aqueous solution of amino acetic acid (containing        4.0 wt % amino acetic acid), wherein the amino acetic acid is in        an amount of 0.05% by weight of the catalyst; then drying at        110° C. for 4 h, evaporating water to obtain a catalyst        supported with amino acetic acid;    -   2. introducing the melted elemental sulfur into the catalyst        containing amino acetic acid in step (1), wherein the elemental        sulfur is in an amount of 105% by weight of the theoretical        sulfur-requiring amount of the catalyst; then adding into the        mixture in which butyl acetate, methyl phenylacetate and        catalytically cracked diesel oil are in a weight ratio of 1:1:8,        wherein the mixture is in an amount of 40% by weight of the        catalyst; and    -   3. treating the catalyst obtained in said step (2) at a normal        pressure, an immobile air atmosphere and a temperature of        110° C. for 4 h, at a temperature of 165° C. for 4 h and at a        temperature of 260° C. for 6 h, to finally obtain the        hydrorefining catalyst EPRES-3 containing the sulfiding agent.

Example 4

The commercial hydrodesulfiding catalyst FH-DS (developed by FushunResearch Institute of Petroleum and Petrochemicals, and produced byWenzhou Huahua Group Co.) was used, and the main components andproperties could be found in Table 2.

The specific presulfurization comprises the steps of

-   -   1. homogeneously impregnating the catalyst FH-DS in oxidation        state into the aqueous solution of amino acetic acid (containing        7.5 wt % amino acetic acid), wherein the amino acetic acid is in        an amount of 9% by weight of the catalyst; then drying at        110° C. for 4 h, evaporating water to obtain a catalyst        supported with amino acetic acid;    -   2. impregnating the catalyst containing organonitrogen compounds        in step (1) with a mixture of peanut oil and lard oil in a        weight ratio of 4:1, wherein the mixture is in an amount of 5%        by weight of the catalyst; then introducing the sublimed        elemental sulfur onto the catalyst in a sealed container,        wherein the elemental sulfur is in an amount of 70% by weight of        the theoretical sulfur-requiring amount of the catalyst; and    -   3. treating the catalyst obtained in said step (2) at a normal        pressure, an immobile air atmosphere and a temperature of        115° C. for 20 min, at a temperature of 145° C. for 12 h and at        a temperature of 270° C. for 2 h, to finally obtain the        hydrorefining catalyst EPRES-4 containing the sulfiding agent.

Example 5

The catalyst in oxidation state was the same as that in Example 4, i.e.FH-DS. The specific presulfurization comprises the steps of

-   -   1. mixing butene dioic acid, t-butylamine and carboamide in a        weight ratio of 1:4:1 together and preparing an aqueous solution        thereof, impregnating the catalyst in oxidation state into the        solution, wherein said substances are in an amount of 4.7% by        weight of the catalyst; then drying at 110° C. for 7 h,        evaporating water to obtain a catalyst containing mixed organic        additives;    -   2. dispersing the elemental sulfur in a solvent in which        kerosene and 1,4-butanediol diacrylate are in a volume ratio of        3:1, wherein the solvent is in an amount of 30% by weight of the        catalyst, and the elemental sulfur is in an amount of 115% by        weight of the theoretical sulfur-requiring amount of the        metal-containing catalyst; then spraying the solvent, in which        the elemental sulfur is dispersed, onto the catalyst in said        step (1); and    -   3. treating the catalyst obtained in said step (2) at a normal        pressure, an immobile air atmosphere and a temperature of        125° C. for 4 h, at a temperature of 165° C. for 6 h and at a        temperature of 250° C. for 7 h, to finally obtain the        hydrorefining catalyst EPRES-5 containing the sulfiding agent.

Example 6

The commercial catalyst 3996 (developed by Fushun Research Institute ofPetroleum and Petrochemicals, and produced by the catalyst factory ofFushun Petrochemical) for hydrogenating heavy oils was used, and themain components and properties could be found in Table 3.

The specific presulfurization comprises the steps of

-   -   1. dissolving a mixture of triethanolamine and        N,N-diethylaminoethanol in a weight ratio of 1:3 in an ammonia        solution containing 6 wt % ammonia, wherein the solution        comprises ammonium sulfide in an amount of 1.0% by weight of the        catalyst; impregnating the catalyst in oxidation state with said        solution, wherein the organonitrogen compound is in an amount of        2.0% by weight of the catalyst; then drying at 140° C. for 5 h,        to obtain a catalyst containing mixed organonitrogen compounds;    -   2. impregnating the catalyst containing organonitrogen compounds        in step (1) with a mixture in which peanut oil and lard oil are        in a weight ratio of 4:1, wherein the mixture is in an amount of        2% by weight of the catalyst; then mixing with the solid powder        of the elemental sulfur, wherein the elemental sulfur is in an        amount of 75% by weight of sulfur-requiring amount calculated        theoretically of the metal-containing catalyst; and    -   3. treating the catalyst obtained in said step (2) at a normal        pressure, an immobile air atmosphere and a temperature of        125° C. for 30 min, at a temperature of 145° C. for 11 h and at        a temperature of 270° C. for 3 h, to finally obtain EPRES-6        containing the sulfiding agent.

Example 7

The catalyst for hydrogenating heavy oils in Example 6 was used. Thespecific presulfurization comprises the steps of

-   -   1. dissolving triethylene diamine in ethanol, wherein the weight        concentration thereof is 10%; spraying said solution onto the        catalyst in oxidation state, wherein triethylene diamine is in        an amount of 8% by weight of the catalyst; then drying at        175° C. for 5 h, to obtain a catalyst containing triethylene        diamine;    -   2. impregnating the catalyst containing organonitrogen compounds        in step (1) with a mixed solvent in which peanut oil and base        lube oil No. 150 are in a weight ratio of 5:1, wherein the mixed        solvent is in an amount of 15% by weight of the catalyst, and        comprises tetramethyl-thiuram-disulfide in an amount of 0.5% by        weight of the catalyst; then introducing the melted elemental        sulfur onto the catalyst, wherein the elemental sulfur is in an        amount of 90% by weight of the theoretical sulfur-requiring        amount of the metal-containing catalyst; and    -   3. treating the catalyst obtained in said step (2) at an        absolute pressure of 0.06 MPa, a naturally mobile air atmosphere        and a temperature of 140° C. for 1 h and at a temperature of        260° C. for 5 h to finally obtain the hydrotreating catalyst        EPRES-7 containing the sulfiding agent.

Example 8

The commercially hydrocracking catalyst 3974 (developed by FushunResearch Institute of Petroleum and Petrochemicals, and produced by thecatalyst factory of Fushun Petrochemical) was used, and the mainproperties could be found in Table 4. The specific presulfurizationcomprises the steps of

-   -   1. dissolving a mixture of triethanolamine and        N,N-diethylaminoethanol in a weight ratio of 1:1 in an ammonia        solution containing 10 wt % ammonia; impregnating the catalyst        in oxidation state with said solution, wherein the        organonitrogen compound is in an amount of 2.5% by weight of the        catalyst; then drying at 160° C. for 4 h, to obtain a catalyst        containing mixed organonitrogen compounds;    -   2. impregnating the catalyst containing organonitrogen compounds        in step (1) with a mixture in which hydrocracked diesel oil,        peanut oil and lard oil are in a weight ratio of 7:2:1, wherein        the mixture is in an amount of 2% by weight of the catalyst;        then introducing the sublimed elemental sulfur onto the catalyst        in a sealed container, wherein the elemental sulfur is in an        amount of 90% by weight of the sulfur-requiring amount        calculated theoretically of the metal-containing catalyst; and    -   3. treating the catalyst obtained in said step (2) at a normal        pressure, an immobile air atmosphere containing 2 v % oxygen and        a temperature of 120° C. for 2 h, at a temperature of 150° C.        for 2 h, at a temperature of 190° C. for 3 h and at a        temperature of 240° C. for 4 h, to finally obtain the        hydrocracking catalyst EPRES-8 containing the sulfiding agent.

Example 9

The commercial hydrodesulfiding catalyst FH-DS (developed by FushunResearch Institute of Petroleum and Petrochemicals, and produced byWenzhou Huahua Group Co.) was used. The main components and propertiescan be found in Table 2. The specific presulfurization comprises thesteps of

-   -   1. homogeneously impregnating the catalyst FH-DS in oxidation        state into the aqueous solution of amino acetic acid (containing        7.5 wt % amino acetic acid), wherein the amino acetic acid is in        an amount of 9% by weight of the catalyst; then drying at        110° C. for 4 h, evaporating water to obtain a catalyst        supported with amino acetic acid;    -   2. dissolving carbon disulfide in a mixed organic solvent        containing peanut oil and catalytically cracked diesel oil in a        weight ratio of 15:1; impregnating the catalyst containing        organonitrogen compounds in step (1) with said solution, wherein        the mixed organic solvent is in an amount of 30% by weight of        the catalyst, and carbon bisulfide is in an amount of 95% by        weight of the sulfur-requiring amount calculated theoretically        of the metal-containing catalyst; and    -   3. treating the catalyst obtained in said step (2) at a normal        pressure, an immobile air atmosphere and a temperature of        115° C. for 20 min, at a temperature of 145° C. for 12 h and at        a temperature of 270° C. for 2 h, to finally obtain the        hydrorefining catalyst EPRES-9 containing the sulfiding agent.

Example 10

By the process in Example 9 except that carbon bisulfide was replacedwith a mixed sulfiding agent in which dimethyl sulfide and thioaceticacid were in a weight ratio of 1:2, the hydrorefining catalyst EPRES-10containing the sulfiding agent was obtained.

Example 11

The process in Example 9 was used, except that step (2) was replacedwith the step of dispersing ammonium sulfide in catalytically crackeddiesel oil, impregnating the catalyst containing organonitrogencompounds in step (1), wherein the catalytically cracked diesel oil wasin an amount of 40% by weight of the catalyst, and ammonium sulfide wasin an amount of 105% by weight of the theoretical sulfur-requiringamount of the metal-containing catalyst.

Other steps and conditions were the same as those in Example 9, so as toobtain the hydrorefining catalyst EPRES-11 containing the sulfidingagent.

The sulfiding agent-containing hydrogenation catalysts obtained in saidexamples and comparative examples were assayed for thesulfur-maintaining ratio and activated, wherein the assay for thesulfur-maintaining ratio was conducted at a pressure of 5.0 MPa, atemperature of 150° C., an H₂/diesel oil volume ratio of 400 (see Table6 for the properties), a liquid hourly volume space velocity of 3.5 h⁻¹,wherein said temperature was maintained for 6 h. The sulfur-maintainingratio was the weight percent of the sulfur maintained after saidtreatment to that of the initial sulfur (see Table 5 for the specificresults).

The procedures for the activation of the sulfiding agent-containinghydrogenation catalysts obtained in said examples and comparativeexamples comprised carrying out in a fixed-bed reactor, the catalyst bedlayer having a height of 800 mm, and the activation conditions could befound in Table 7. The results of the maximum temperature rise at theoutlet and inlet of the bed layer during the activation of varioussulfur-containing catalysts could be found in Table 8. The inlet andoutlet temperature curves of the catalyst EPRES-2 during the temperaturerise could be found in FIG. 1, and the inlet and outlet temperaturecurves of the catalyst C-EPRES-2 in the comparative examples during thetemperature rise could be found in FIG. 2. In addition, the results ofand C-EPRES-2 for hydrogenation of diesel oil fraction could be found inTable 9.

TABLE 1 Main components and properties of FH-5A hydrodesulfurizationcatalyst Catalyst FH-5A in oxidation state Support Al₂O₃ Active metalcomponents, wt % MoO₃ 24.3 NiO 4.2 Auxiliary agent SiO₂, wt % 10.1 Porevolume, ml · g⁻¹ 0.4 Specific surface area, m² · g⁻¹ 190

TABLE 2 Main components and properties of FH-DS hydrodesulfurizationcatalyst Catalyst FH-DS in oxidation state Support Al₂O₃ Active metalcomponents, wt % WO₃ 19.3 MoO₃ 6.7 NiO 2.2 CoO 3.4 Pore volume, ml · g⁻¹0.32 Specific surface area, m² · g⁻¹ 170

TABLE 3 Main components and properties of the catalyst 3996 forhydrotreating heavy oils Catalyst 3996 in oxidation state Support Al₂O₃Active metal components, wt % MoO₃ 23.9 NiO 4.2 Auxiliary agent P₂O₅, wt% 3.8 Pore volume, ml · g⁻¹ 0.35 Specific surface area, m² · g⁻¹ 173

TABLE 4 Main properties and components of hydrocracking catalyst 3974Catalyst 3974 in oxidation state Support, wt % Al₂O₃ balance Amorphoussilica-alumina containing 35 40 wt % of SiO₂ Modified Y molecular sieve(wherein 15 the molar ratio of SiO₂/Al₂O₃ is 13) Active metalcomponents, wt % WO₃ 28.2 NiO 4.2 Pore volume, ml · g⁻¹ 0.40 Specificsurface area, m² · g⁻¹ 240

TABLE 5 Sulfur-maintaining ratio of the sulfiding agent-containinghydrogenation catalyst in the Examples and Comparative Examples SerialNo. Sulfur-containing catalysts Sulfur-maintaining ratio, % Example 1EPRES-1 62.9 Example 2 EPRES-2 68.5 Comparative C-EPRES-2 52.6 Example 1Example 3 EPRES-3 78.1 Example 4 EPRES-4 74.2 Example 5 EPRES-5 67.8Example 6 EPRES-6 76.9 Example 7 EPRES-7 71.8 Example 8 EPRES-8 75.2Example 9 EPRES-9 85.7 Example 10 EPRES-10 89.4 Example 11 EPRES-11 76.9

TABLE 6 Properties of diesel oil used for sulfur-maintaining ratio assayand activation Raw oils Diesel oil Gasoline Density (20° C.), kg · m⁻³830.5 723.2 Final boiling point (20° C.) 352 165 Sulfur, μg · g⁻¹ 687105 Nitrogen, μg · g⁻¹ 116.7 1.4 Acidity, mgKOH · (100 mL)⁻¹ 5.53 /

TABLE 7 Conditions for the activtion of the sulfiding agent-containinghydrogenation catalysts in the Examples and Comparative ExamplesPressure (MPa)/ratio of hydrogen to oil/ Time of liquid hourly Rate ofFinally risen maintaining Activation space velocity temperaturetemperature constant Examples No. materials (h⁻¹) rise (° C./h) (° C.)temperature Example 1 Gasoline 2/300/1 10 220 5 Example 2 Diesel oil6/500/3 30 300 12 Comparative Diesel oil 6/500/3 30 300 12 Example 1Example 3 Diesel oil 6/800/2 60 320 24 Example 4 Diesel oil 8/800/2 80320 18 Example 5 Diesel oil 8/800/2 50 280 18 Example 6 Diesel oil15/1200/5 40 280 24 Example 7 Diesel oil 15/1200/7 30 300 24 Example 8 /15/25000 (H₂ 60 350 3 volume flow rate, h⁻¹) Example 9 Diesel oil8/800/2 90 350 15 Example 10 Diesel oil 8/800/2 90 340 12 Example 11Diesel oil 8/800/2 40 280 35

TABLE 8 Maximum temperature rise of the bed layer during the activationof the sulfiding agent-containing hydrogenation catalysts in theExamples and Comparative Examples Sulfur-containing Maximum temperaturerise of the Serial No. catalyst bed layer during the activation, ° C.Example 1 EPRES-1 14 Example 2 EPRES-2 12 Comparative C-EPRES-2 24Example 1 Example 3 EPRES-3 12 Example 4 EPRES-4 12 Example 5 EPRES-5 11Example 6 EPRES-6 9 Example 7 EPRES-7 11 Example 8 EPRES-8 11 Example 9EPRES-9 9 Example 10 EPRES-10 8 Example 11 EPRES-11 12

TABLE 9 Conditions and results of EPRES-2 and C-EPRES-2 forhydrogenating diesel oil fraction Catalysts EPRES-2 C-EPRES-2 Feedstocksand products Hydro- Refined oil cracked diesel oil Reaction temperature,° C. 340 340 Reaction pressure, MPa 6.0 6.0 Hydrogen/oil ratio 350 350Liquid hourly space velocity, h⁻¹ 3.0 3.0 Density (20° C.), g · cm⁻³0.9334 0.9420 0.9458 Final boiling point, ° C. 355 354 353 Sulfur, μg ·g⁻¹ 10766 1052 3284 Nitrogen, μg · g⁻¹ 767 80.5 127.0

Example 12

The processing conditions and results of EPRES-1 for hydrorefininggasoline fraction are shown in Table 10.

TABLE 10 Conditions and results of EPRES-1 for hydrorefining gasolinefraction Catalyst EPRES-1 Feedstock and products Distilled gasolineRefined oil Reaction temperature, ° C. 260 Reaction pressure, MPa 2.0Hydrogen/oil ratio 150 Liquid hourly space velocity, h⁻¹ 18 Density (20°C.), g · cm⁻³ 0.7232 0.7183 Sulfur, μg · g⁻¹ 105 <0.5 Nitrogen, μg · g⁻¹1.4 <0.5

Example 13

The processing conditions and results of EPRES-3, EPRES-4 and EPRES-5for hydrorefining diesel oil fraction are shown in Table 11.

TABLE 11 Conditions and results of EPRES-3, EPRES-4 and EPRES-5 forhydrorefining diesel oil fraction Catalysts EPRES-3 EPRES-4 EPRES-5Feedstock and products Refined Mixed Refined Catalyzed Refined Coked oiloil diesel oil oil oil oil Reaction 350 340 370 temperature, ° C.Reaction pressure, 6.0 8.0 6.0 MPa Hydrogen/oil ratio 800 1000 1200Liquid hourly space 3.0 2.5 2.0 velocity, h⁻¹ Density (20° C.), 0.81850.7911 0.8516 0.8275 0.9022 0.8674 g · cm⁻³ Distillation range, 178-365170-360 181-370 173-365 167-363 148-359 ° C. Sulfur, μg · g⁻¹ 846 259200 12 10530 11 Nitrogen, μg · g⁻¹ 1102 37 285 <1 909 12

Example 14

The processing conditions and results of EPRES-6 and EPRES-7 forhydrorefining vacuum gas oil are shown in Table 12.

TABLE 12 Conditions and results of EPRES-6 and EPRES-7 for hydrogenatingvacuum gas oil (VGO) Catalysts EPRES-6 EPRES-7 Feedstocks and productsVGO Refined Refined oil oil Reaction temperature, ° C. 370 390 Reactionpressure, MPa 15 15 Hydrogen/oil ratio 1500 1500 Liquid hourly spacevelocity, h⁻¹ 1.0 2.0 Density (20° C.), g · cm⁻³ 0.9021 0.8970 0.8970Distillation range, ° C. 281-538 274-530 274-530 Sulfur, μg · g⁻¹ 155002.0 1.8 Nitrogen, μg · g⁻¹ 13880 3.2 3.1

Example 15

The processing conditions and results of EPRES-8 for hydrocrackingvacuum gas oil were shown in Table 13. Said vacuum gas oil had adistillation range of 352-535° C., a sulfur-content of 1.95 wt %, anitrogen-content of 1280 μg/g. Said vacuum gas oil was firstlyhydrorefined with EPRES-7 to an extent of a nitrogen-content less than 5μg/g, and then hydrocracked.

TABLE 13 Conditions and results of EPRES-8 for hydrocracking vacuum gasoil Catalyst EPRES-8 Operating conditions Reaction temperature, ° C. 375Reaction pressure, MPa 15 Hydrogen/oil ratio 3000 Liquid hourly spacevelocity, h⁻¹ 1.5 Yields and properties of main products Yield ofaviation kerosene (177-282° C.), wt % 20.2 Smoke point of aviationkerosene, mm 30 Yield of diesel oil (282-370° C.), wt % 35.1 Cetanevalue of diesel oil 61 Yield of tail oil (>370° C.), wt % 31.2 BMCIvalue of tail oil 6.5

Example 16

The processing conditions and results of EPRES-9, EPRES-10 and EPRES-11for hydrorefining diesel oil fraction were shown in Table 14.

TABLE 14 Conditions and results of EPRES-9, EPRES-10 and EPRES-11 forhydrorefining diesel oil fraction Catalysts EPRES-9 EPRES-10 EPRES-11Feedstocks and products Mixed Catalyzed Coked oil Refined oil diesel oilRefined oil oil Refined oil Reaction 350 340 370 temperature, ° C.Reaction pressure, 6.0 8.0 6.0 MPa Hydrogen/oil ratio 800 1000 1200Liquid hourly space 3.0 2.5 2.0 velocity, h⁻¹ Density (20° C.), 0.81850.7902 0.8516 0.8273 0.9022 0.8670 g · cm⁻³ Distillation 178-365 170-360181-370 173-365 167-363 148-359 range, ° C. Sulfur, μg · ⁻¹ 846 12 920012 10530 11 Nitrogen, μg · g⁻¹ 1102 <1 285 <1 909 <1

1. A hydrogenation catalyst composition, comprising (1) a hydrogenationcatalyst; (2) an organonitrogen compound containing 1-15 carbon atoms,which is in an amount of 0.01%-20% by weight of the catalyst; (3) asulfiding agent; and (4) an organic solvent, wherein said organonitrogencompound is selected from one or more substances of hydrocarbyl amines,alcohol amines and amino acids.
 2. The composition according to claim 1,characterized in that the sulfiding agent is selected from the groupconsisting of the elemental sulfur, organic sulfides, inorganicsulfides, and mixtures thereof.
 3. The composition according to claim 1,characterized in that the sulfiding agent is in an amount of 30%-150% byweight of the theoretical sulfur-requiring amount of the hydrogenationcatalyst; and the organic solvent is in an amount of 0.1%-50% by weightof the catalyst.
 4. The composition according to claim 1, characterizedin that the organonitrogen compound is in an amount of 2.0%-10% byweight of the catalyst; the sulfiding agent is in an amount of 55%-120%by weight of the theoretical sulfur-requiring amount of thehydrogenation catalyst; and the organic solvent is in an amount of15%-30% by weight of the catalyst.
 5. The composition according to claim1, characterized in that the hydrogenation catalyst comprises refractoryinorganic oxides as the support, and one or more metals selected fromthe group consisting of W, Mo, Ni and Co as active metal components. 6.The composition according to claim 1, characterized in that theorganonitrogen compound contains 2-10 carbon atoms.
 7. The compositionaccording to claim 1, characterized in that the organonitrogen compoundis an amino acid substance.
 8. The composition according to claim 1,characterized in that the organonitrogen compound is selected from oneor more substances of ethylene diamine, ethanolamine, diethanolamine,triethanolamine, diisopropanolamine, triethylamine,2-cyclohexanediamine, trimethylene diamine, triethylene diamine,triethylene tetramine, t-butylamine, dodecyl amine, trioctylamine,ammonium tri-isopropionate, N,N-diethyl ethanolamine, aminononanoicacid, amino acetic acid, nitrilotriacetic acid, N,N-diethylhydroxylamine, N-methyl diethanolamine, hexamethylene tetramine,N,N-diisopropyl ethanolamine, acetanilide, N,N-dihydroxyethylaniline,glutamic acid, and other substance(s) having similar structures to saidsubstances above.
 9. The composition according to claim 1, characterizedin that the organonitrogen compound is an organic substancesimultaneously containing nitrogen and oxygen.
 10. The compositionaccording to claim 1, characterized in that the organic solvent isselected from one or more substances of hydrocarbon oils and organiccarboxylic esters.
 11. The composition according to claim 10,characterized in that the hydrocarbon oils are selected from one or moresubstances of naphtha, gasoline, kerosene, diesel oil, white oil, lubebase oil, distilled and vacuum heavy distillate oil; and the organiccarboxylic esters are organic carboxylic esters containing from 6-60carbon atoms.
 12. The composition according to claim 10, characterizedin that the hydrocarbon oils are obtained by the catalytic crackingprocess or the thermal cracking process; and the organic carboxylicesters are selected from one or more substances of sesame oil, safflowerseed oil, corn oil, cottonseed oil, peanut oil, rape-seed oil, bean oil,walnut oil, cocoanut oil, olive oil, sunflower seed oil, lard oil,n-butyl acetate, propylene glycol acetate monomethyl ether,1,4-butanediol diacrylate, isopropyl cyclohexanoate,hexamethylene-diisocyanate, triethyl phosphate, methyl phenylacetate,isobutyl phenylacetate, diisononyl terephthalate, dimethyl phthalate,diethyl phthalate, methyl o-hydroxybenzoate, and butylp-hydroxybenzoate.
 13. The composition according to claim 10,characterized in that the hydrocarbon oils and organic carboxylic estersare mixed in a weight ratio of 1:15-15:1.
 14. A process for preparing ahydrogenation catalyst composition, comprising the steps of (1)supporting an organonitrogen compound onto the hydrogenation catalyst inoxidation state, wherein the organonitrogen compound is in an amount of0.01%-20% by weight of the catalyst; and (2) supporting an organicsolvent and sulfiding agent onto the hydrogenation catalyst containingthe organonitrogen compound in step (1).
 15. The process according toclaim 14, characterized in that the sulfiding agent is selected from thegroup consisting of the elemental sulfur, organic sulfides, inorganicsulfides, and mixtures thereof.
 16. The process according to claim 14,characterized in that the sulfiding agent is in an amount of 30%-150% byweight of the theoretical sulfur-requiring amount of the hydrogenationcatalyst; and the organic solvent is in an amount of 0.1%-50% by weightof the catalyst.
 17. The process according to claim 14, characterized inthat the catalyst composition obtained in step (2) is heat-treated. 18.The process according to claim 17, characterized in that the catalystcomposition is heat-treated for 0-20 h at 100-130° C., then for 0.2-15 hat 130-180° C., and finally for 0-15 h at 180-300° C.
 19. The processaccording to claim 18, characterized in that the heat-treatment lasts0.2-15 h at 100-130° C., then 0.2-15 h at 130-180° C., and finally 1-8 hat 180-300° C.
 20. The process according to claim 14, characterized inthat the organonitrogen compound in step (1) is supported by animpregnating method comprising formulating an aqueous solution, ammoniasolution or organic solution with the organonitrogen compound, andimpregnating the hydrogenation catalyst, and then drying to removewater, ammonia or organic solvent to obtain the hydrogenation catalystsupported with the organonitrogen compound; or by directly introducingthe organonitrogen compound onto the hydrogenation catalyst.
 21. Theprocess according to claim 14, characterized in that the organic solventand sulfiding agent in step (2) are supported by (1) firstly supportingthe sulfiding agent onto the catalyst, then impregnating with theorganic solvent; (2) dispersing the sulfiding agent into the organicsolvent, and then introducing onto the catalyst; or (3) impregnating thecatalyst with the organic solvent first, and then introducing thesulfiding agent.
 22. A hydrogenating process, comprising the steps of:(A) feeding the hydrogenation catalyst composition of claim 1 into areactor; (B) activating the hydrogenation catalyst; and (C) contacting ahydrocarbon oil with the hydrogenation catalyst under suitableconditions to hydrogenate the hydrocarbon oil.
 23. The process accordingto claim 22, characterized in that the hydrogenating process is selectedfrom the hydrorefining process, hydrocracking process andhydro-upgrading process of hydrocarbons.
 24. The process according toclaim 22, characterized in that the activation in step (B) is conductedat a pressure of 1-20 MPa, an H₂ space velocity of 100-30,000 h⁻¹, arate of temperature rise of 5-100° C./h, a final temperature at theinlet of the reactor of 200-400° C., wherein said final temperature ismaintained for 2-36 h.
 25. The process according to claim 24,characterized in that one or more distillate oils selected fromgasoline, kerosene and diesel oil are added during the activation,wherein the liquid hourly space velocity of the distillate oils is0.2-20 h⁻¹, and the H₂/oil volume ratio is 100:1-2,000:1.
 26. Theprocess according to claim 22, characterized in that the hydrogenationin step (C) is carried out at a pressure of 1-20 MPa, a temperature of100-450° C., an H₂/oil volume ratio of 50-3,000, and a liquid hourlyspace velocity of 0.1-30 h⁻¹.
 27. Use of the hydrogenation catalyst inclaim 1 in hydrorefining, hydrocracking or hydro-upgrading hydrocarbons.